Modified poly(phenylene ether) copolymers, compositions, and methods thereof

ABSTRACT

A poly(phenylene ether) copolymer comprising first repeating units comprising a C 1-6 alkyl(C 6-30 cycloalkenyl) pendant group; second repeating units different from the first repeating units; a copolymer of Formula (3); and optionally, at least one terminal functional group comprising (meth)acrylate, styrene, —CH 2 —(C 6 H 4 )—CH═CH 2 , allyl, cyanate ester, glycidyl ether, anhydride, aniline, maleimide, an activated ester, or a combination thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to European Application No. 20165893.7filed on Mar. 26, 2020, the content of which is herein incorporated byreference in its entirety.

BACKGROUND

This disclosure relates to poly(phenylene ether) copolymers, and inparticular to modified poly(phenylene ether) copolymers, poly(phenyleneether) copolymer compositions, methods of manufacture, and uses thereof.

Thermosetting resins are materials that cure to form very hard plastics.These materials that can be used in a wide variety of consumer andindustrial products. For example, thermosets are used in protectivecoatings, adhesives, electronic laminates (such as those used in thefabrication of computer circuit boards), flooring, and pavingapplications, glass fiber-reinforced pipes, and automotive parts(including leaf springs, pumps, and electrical components).Poly(polyphenylene ether)s generally have good dielectric properties.Because of their broad use, particularly in electronic applications,such as laminates for printed circuit boards, it is desirable to providethermoset compositions including poly(phenylene ether) copolymers withhigh glass transition temperatures while maintaining or improving thedielectric properties.

There accordingly remains a need in the art for poly(polyphenyleneether)s that have high glass transition temperatures. It would be afurther advantage if the poly(polyphenylene ether)s had improveddielectric properties.

SUMMARY

The above-described and other deficiencies of the art are met by apoly(phenylene ether) copolymer comprising first repeating unitscomprising a C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group; secondrepeating units different from the first repeating units; a copolymer ofFormula (3a); and optionally, at least one terminal functional groupcomprising (meth)acrylate, styrene, —CH₂—(C₆H₄)—CH═CH₂, allyl, cyanateester, glycidyl ether, anhydride, aniline, maleimide, an activatedester, or a combination thereof,

wherein, in the formula (3a), each occurrence of Q¹ and Q² independentlycomprise halogen, unsubstituted or substituted C₁₋₁₂ primary orsecondary hydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; eachoccurrence of Q³ and Q⁴ independently comprise hydrogen, halogen,unsubstituted or substituted C₁-C₁₂ primary or secondary hydrocarbyl,C₁-C₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; x and yare each independently 0-30; optionally, at least one of Q¹ to Q⁴ isunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); L is of theformula

wherein each occurrence of R³, R⁴, R⁵, and R⁶ is independently hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; w is 0 or1; and Y is

wherein each occurrence of R⁷ is independently hydrogen or C₁₋₁₂hydrocarbyl, each occurrence of R⁸ and R⁹ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or R⁸ and R⁹ together form a C₄₋₁₂cyclohydrocarbylene with the carbon atom; or L is of the formula

wherein E is 6-100, each occurrence of R is independently anunsubstituted or substituted C₁₋₁₃ alkyl, C₁₋₁₃ alkoxy, C₃₋₆ cycloalkyl,C₃₋₆ cycloalkoxy, C₆₋₁₄ aryl, C₆₋₁₀ aryloxy, C₇₋₁₃ arylalkylene, orC₇₋₁₃ alkylarylene; each p and q are independently 0 or 1, R¹ is adivalent C₂₋₈ aliphatic group, each occurrence of M is independentlyhalogen, cyano, nitro, C₁₋₈ alkylthio, C₁₋₈ alkyl, C₁₋₈ alkoxy, C₂₋₈alkenyl, C₂₋₈ alkenyloxy, C₃₋₈ cycloalkyl, C₃₋₈ cycloalkoxy, C₆₋₁₀ aryl,C₆₋₁₀ aryloxy, C₇₋₁₂ aralkyl, C₇₋₁₂ aralkoxy, C₇₋₁₂ alkylaryl, or C₇₋₁₂alkylaryloxy, and each n is independently 0, 1, 2, 3, or 4.

In another aspect, a method of manufacture comprises making theabove-described poly(phenylene ether) copolymer.

In another aspect, a curable composition comprises the above-describedpoly(phenylene ether) copolymer.

In another aspect, a thermoset composition comprises the above-describedcurable composition.

In another aspect, an article comprises the above-described thermosetcomposition.

The above-described and other features are exemplified by the followingdrawings, detailed description, examples, and claims.

DETAILED DESCRIPTION

The inventor hereof has discovered that the introduction of bulky,non-polar substituents as pendant groups on poly(phenylene ether)copolymers can increase the glass transition temperature of thepoly(phenylene ether) copolymer, while maintaining or improving thedielectric properties of the poly(phenylene ether) copolymers. The bulkygroups include C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) groups derived from acycloaddition reaction of an alkene or alkyne with a conjugated diene.As used herein, the term C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) refers to anC₁₋₆-alkylene group with a C₆₋₃₀cycloalkenyl substituent, wherein theC₆₋₃₀cycloalkenyl substituent has at least one double bond. TheC₆₋₃₀cycloalkenyl substituent can be a single ring, a fused ring system,or a bicyclic ring system.

The poly(phenylene ether) copolymer comprises: first repeating unitscomprising a C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group; secondrepeating units; a copolymer of Formula (3a); and optionally, at leastone terminal functional group comprising (meth)acrylate, styrene,—CH₂—(C₆H₄)—CH═CH₂, allyl, cyanate ester, glycidyl ether, anhydride,aniline, maleimide, an activated ester, or a combination thereof. Theindividual components of the poly(phenylene ether) copolymers aredescribed in detail below.

The poly(polyphenylene ether) copolymers include first repeating unitsof formula (1)

wherein each occurrence of Z¹ comprises halogen, unsubstituted orsubstituted C₁₋₁₂ primary or secondary hydrocarbyl, C₁₋₁₂hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), orC₂₋₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms, and each occurrence of Z² comprises hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂-C₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; and atleast one of Z¹ and Z² is an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) group.

In an aspect in formula (1), each occurrence of Z¹ comprises halogen,unsubstituted or substituted C₁₋₆ primary or secondary hydrocarbyl, C₁₋₆hydrocarbylthio, C₁₋₆ hydrocarbyloxy, C₁₋₃alkyl(C₆₋₁₂cycloalkenyl), orC₂-C₇ halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms, and each occurrence of Z² comprises hydrogen,halogen, unsubstituted or substituted C₁₋₆ primary or secondaryhydrocarbyl, C₁₋₆ hydrocarbylthio, C₁₋₆ hydrocarbyloxy,C₁₋₃alkyl(C₆₋₁₂cycloalkenyl), or C₂-C₇ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; and atleast one of Z¹ and Z² is an unsubstituted or substitutedC₁₋₃alkyl(C₆₋₁₂cycloalkenyl) group.

In a more preferred aspect, each occurrence of Z¹ comprises halogen,unsubstituted or substituted C₁₋₆ primary or secondary hydrocarbyl, C₁₋₆hydrocarbylthio, C₁₋₆ hydrocarbyloxy, C₁alkyl(C₆₋₁₂cycloalkenyl), orC₂-C₇ halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms, and each occurrence of Z² comprises hydrogen,halogen, or unsubstituted or substituted primary C₁₋₆ hydrocarbyl,C₁alkyl(C₆₋₁₂cycloalkenyl); and at least one of Z¹ and Z² is anunsubstituted or substituted C₁alkyl(C₆₋₁₂ cycloalkenyl) group.

The C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group of the first repeatingunit can include a —C₁-C₃alkyl(bicyclo[2.2.1]heptene) group, a—C₁-C₃alkyl(bicyclo[2.2.1]heptadiene) group, a —C₁-C₃alkyl(cyclohexene)group, a —C₁-C₃alkyl(cyclohexadiene) group, or a —C₁-C₃alkyl(C₆₋₃₀cycloalkenyl) group, wherein the C₆₋₃₀ cycloalkenyl group is derivedfrom a terpene, each optionally substituted with a C₁₋₁₂ primary orsecondary hydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or acombination thereof. In some aspects, the C₁₋₆alkyl(C₆₋₃₀cycloalkenyl)pendant group of the first repeating unit includes a—C₁-C₃alkyl(bicyclo[2.2.1]heptene) group, a —C₁-C₃alkyl(cyclohexene)group, or a combination thereof. In some aspects, theC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group of the first repeating unitincludes a —C₁-C₃alkyl(bicyclo[2.2.1]heptadiene) group, a—C₁-C₃alkyl(cyclohexadiene) group, or a combination thereof. In someaspects, the C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group of the firstrepeating unit includes a —C₁-C₃alkyl(bicyclo[2.2.1]heptene) group, a—C₁-C₃alkyl(cyclohexene) group, or a —C₁-C₃alkyl(C₆₋₃₀ cycloalkenyl)group, wherein the C₆₋₃₀ cycloalkenyl group is derived from a terpene,or a combination thereof. In some aspects, theC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group of the first repeating unitincludes a —C₁-C₃alkyl(bicyclo[2.2.1]heptadiene) group, a—C₁-C₃alkyl(cyclohexadiene) group, or a —C₁-C₃alkyl(C₆₋₃₀ cycloalkenyl)group, wherein the C₆₋₃₀ cycloalkenyl group is derived from a terpene,or a combination thereof. In any of the foregoing, the pendant groupscan be substituted with a C₁₋₁₂ primary or secondary hydrocarbyl, C₁₋₁₂hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or a combination thereof,preferably a C₁₋₆ primary or secondary hydrocarbyl, C₁₋₆hydrocarbylthio, C₁₋₆ hydrocarbyloxy, or a combination thereof, morepreferably a C₁₋₃ primary or secondary hydrocarbyl, C₁₋₃hydrocarbylthio, C₁₋₃ hydrocarbyloxy, or a combination thereof.

In particular aspects, the first repeating units can be derived from2-CH₂(C₆₋₃₀cycloalkenyl)-6-methyl phenol,2-CH₂(C₆₋₃₀cycloalkenyl)-3,6-dimethyl phenol,3-CH₂(C₆₋₃₀cycloalkenyl)-2,6-dimethyl phenol,2-phenyl-6-CH₂(C₆₋₃₀cycloalkenyl) phenol, or a combination thereof;preferably 2-CH₂(C₆₋₁₂cycloalkenyl)-6-methyl phenol, 2-CH₂(C₆₋₁₂cycloalkenyl)-3,6-dimethyl phenol, 3-CH₂(C₆₋₁₂cycloalkenyl)-2,6-dimethylphenol, 2-phenyl-6-CH₂(C₆₋₁₂cycloalkenyl) phenol, or a combinationthereof.

In addition to the first repeating units, the poly(polyphenylene ether)copolymer includes second repeating units of formula (2)

wherein Z³ and Z⁴ are each independently hydrogen, halogen,unsubstituted or substituted C₁₋₁₂ primary or secondary hydrocarbyl,C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or C₂-C₁₂halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms.

In a preferred aspect in formula (2), Z³ and Z⁴ are each independentlyhydrogen, halogen, unsubstituted or substituted C₁₋₆ primary orsecondary hydrocarbyl, C₁₋₆ hydrocarbylthio, C₁₋₆ hydrocarbyloxy, orC₂-C₇ halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms.

In a more preferred aspect of formula (2), Z³ and Z⁴ are eachindependently hydrogen, halogen, or unsubstituted or substituted primaryC₁₋₆ hydrocarbyl. In some aspects, the second repeating units arederived from 2,6-dimethyl phenol, 2,3,6-trimethyl phenol,2-phenyl-6-methyl phenol, 2-allyl-6-methyl phenol, or a combinationthereof.

The poly(polyphenylene ether) copolymers include first repeating unitsand second repeating units. A molar ratio of first repeating units tosecond repeating units can range from 1:99 to 99:1, 10:90 to 90:10,20:80 to 80:20, 25:75 to 75:25, 70:30 to 30:70, 60:40 to 40:60, or50:50, each based on the total moles of first repeating units and secondrepeating units.

The poly(polyphenylene ether) copolymers can comprise units havingaminoalkyl-containing end group(s), typically located in a positionortho to the hydroxy group. Also frequently present aretetramethyldiphenoquinone (TMDQ) end groups, typically obtained from2,6-dimethylphenol-containing reaction mixtures in whichtetramethyldiphenoquinone by-product is present. Thus, Z¹ and Z² caneach independently be hydrogen, cyclohexyl, phenyl,di-n-butylaminomethyl, morpholinomethyl or a combination thereof. In apreferred aspect, the poly(polyphenylene ether) copolymer comprises2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenyleneether units, or a combination thereof. In some aspects, thepoly(polyphenylene ether) copolymer comprisespoly(2,6-dimethyl-1,4-phenylene ether) units.

In addition to the first repeating units of Formula (1) and the secondrepeating units of Formula (2), the poly(polyphenylene ether) copolymerincludes a copolymer of Formula (3)

wherein each occurrence of Q¹ and Q² independently comprises halogen,unsubstituted or substituted C₁₋₁₂ primary or secondary hydrocarbyl,C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; eachoccurrence of Q³ and Q⁴ independently comprises hydrogen, halogen,unsubstituted or substituted C₁-C₁₂ primary or secondary hydrocarbyl,C₁-C₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; x and yhave an average value, and are each independently 0-30, or 0-20,preferably 0-15, still more preferably 0-10, even more preferably 0-8,provided that the sum of x and y is at least 2, preferably at least 3,more preferably at least 4. In some aspects, at least one of Q¹, Q², Q³,and Q⁴ is an unsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl),preferably an unsubstituted or substituted C₁₋₃alkyl(C₆₋₁₂cycloalkenyl),more preferably an unsubstituted or substitutedC₁alkyl(C₆₋₁₂cycloalkenyl).

The poly(polyphenylene ether) copolymer can include at least oneterminal functional group. In some aspects, the poly(polyphenyleneether) copolymer can be monofunctional, having a terminal functionalgroup at one terminus of the poly(polyphenylene ether) copolymer chain.The terminal functional group can be, for example, (meth)acrylate,styrene, —CH₂—(C₆H₄)—CH═CH₂, allyl, cyanate ester, glycidyl ether,anhydride, aniline, maleimide, or an activated ester. Thepoly(polyphenylene ether) copolymer can be bifunctional, having terminalfunctional groups at both termini of the poly(polyphenylene ether)copolymer chain. The terminal functional groups comprise (meth)acrylate,styrene, —CH₂—(C₆H₄)—CH═CH₂, allyl, cyanate ester, glycidyl ether,anhydride, aniline, maleimide, an activated ester, or a combinationthereof.

Further in formula (3), L is of formula (4) or formula (5) as describedbelow. L can be of formula (4)

wherein each occurrence of R³, R⁴, R⁵, and R⁶ is independently hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; w is 0 or1; and Y is

wherein each occurrence of R⁷ is independently hydrogen or C₁₋₁₂hydrocarbyl, each occurrence of R⁸ and R⁹ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or R⁸ and R⁹ together form a C₄₋₁₂cyclohydrocarbylene with the carbon atom. In a preferred aspect informula (4), each of R³, R⁴, R⁵, and R⁶ is independently hydrogen,halogen, unsubstituted or substituted C₁₋₆ primary or secondaryhydrocarbyl, or C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), and w is 0 or 1. In someaspects, when L is formula (4), at least one of Q¹, Q², Q³, and Q⁴ offormula (3), at least one of R³, R⁴, R⁵, and R⁶ of formula (4), or acombination thereof is an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl), preferably an unsubstituted or substitutedC₁₋₃alkyl(C₆₋₁₂cycloalkenyl), more preferably an unsubstituted orsubstituted C₁alkyl(C₆₋₁₂cycloalkenyl).

In another aspect, L in formula (3) is of formula (5)

wherein E is 6-100, or 11-80, or 11-60; and each occurrence of R isindependently an unsubstituted or substituted C₁₋₁₃ alkyl, C₁₋₁₃ alkoxy,C₃₋₆ cycloalkyl, C₃₋₆ cycloalkoxy, C₆₋₁₄ aryl, C₆₋₁₀ aryloxy, C₇₋₁₃arylalkylene, or C₇₋₁₃ alkylarylene. The foregoing groups can be fullyor partially halogenated with fluorine, chlorine, bromine, or iodine, ora combination thereof. Further in formula (5), each p and q areindependently 0 or 1; R¹ is a divalent C₂₋₈ aliphatic group, and eachoccurrence of M is independently halogen, cyano, nitro, C₁₋₈ alkylthio,C₁₋₈ alkyl, C₁₋₈ alkoxy, C₂₋₈ alkenyl, C₂₋₈ alkenyloxy, C₃₋₈ cycloalkyl,C₃₋₈ cycloalkoxy, C₆₋₁₀ aryl, C₆₋₁₀ aryloxy, C₇₋₁₂ aralkyl, C₇₋₁₂aralkoxy, C₇₋₁₂ alkylaryl, or C₇₋₁₂ alkylaryloxy, wherein each n isindependently 0, 1, 2, 3, or 4. Preferably in formula 4, E is 5-60; eachoccurrence of R is independently C₁₋₆ alkyl, C₃₋₆ cycloalkyl, or C₆₋₁₄aryl, more preferably methyl; p and q are each 1; R¹ is a divalent C₂₋₈aliphatic group, M is halogen, cyano, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₆₋₁₀aryl, C₇₋₁₂ aralkyl, or C₇₋₁₂ alkylaryl, more preferably methyl ormethoxy; and each n is independently 0, 1, or 2. In some aspects, when Lis of formula (5), at least one of Q¹, Q², Q³, and Q⁴ of formula (3) isunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), preferablyunsubstituted or substituted C₁₋₃alkyl(C₆₋₁₂cycloalkenyl), morepreferably unsubstituted or substituted C₁alkyl(C₆₋₁₂cycloalkenyl).

In some aspects, L is of formula (4a)

wherein n has an average value of 5-100, or 10-80, or 10-60. In someaspects, when L is of formula (4a), at least one of Q¹, Q², Q³, and Q⁴of formula (3) is an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl), preferably an unsubstituted or substitutedC₁₋₃alkyl(C₆₋₁₂ cycloalkenyl), more preferably unsubstituted orsubstituted C₁alkyl(C₆₋₁₂cycloalkenyl).

In an aspect, the poly(polyphenylene ether) copolymer comprises apoly(polyphenylene ether) copolymer of formula (3a)

wherein Q¹, Q², Q³, Q⁴, L, x and y are as defined in formulas (3), (4),or (5). In an aspect, Q¹, Q², Q³, or Q⁴ is hydrogen, methyl, cyclohexyl,phenyl, di-n-butylaminomethyl, morpholinomethyl, or unsubstituted orsubstituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl). In some aspects, at least oneof Q¹, Q², Q³, and Q⁴ is an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl, preferably unsubstituted or substitutedC₁₋₃alkyl(C₆₋₁₂cycloalkenyl), more preferably unsubstituted orsubstituted C₁alkyl(C₆₋₁₂cycloalkenyl).

The poly(polyphenylene ether) copolymer can include poly(polyphenyleneether) copolymer of formula (3b)

wherein each occurrence of Q⁵ and Q⁶ is independently methyl,cyclohexyl, phenyl, di-n-butylaminomethyl, morpholinomethyl, anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); and eachoccurrence of a and b is independently 0-20, with the proviso that thesum of a and b is at least 2. In some aspects, at least one of Q⁵ and Q⁶is unsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl). In someaspects, in formula (3b), each occurrence of Q⁵ and Q⁶ is independentlymethyl, cyclohexyl, phenyl, di-n-butylaminomethyl, morpholinomethyl,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); and at least one of Q⁵ and Q⁶ isunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); preferablyunsubstituted or substituted C₁₋₃alkyl(C₆₋₁₂cycloalkenyl), morepreferably unsubstituted or substituted C₁alkyl(C₆₋₁₂cycloalkenyl).Poly(polyphenylene ether) copolymers of this type wherein theC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) groups are absent are commerciallyavailable, for example NORYL SA9000, from SABIC.

The poly(polyphenylene ether) copolymer can further include anaryloxy-terminated polysiloxane block having repeating siloxane units offormula (6)

wherein each occurrence of R³ is independently C₁₋₁₂ hydrocarbyl orC₁₋₁₂ halohydrocarbyl; and the polysiloxane block further comprises aterminal unit of formula (7)

wherein Y is hydrogen, halogen, C₁₋₁₂ hydrocarbyl, or C₁₋₁₂hydrocarbyloxy, and each occurrence of R³ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or C₁₋₁₂ halohydrocarbyl. Preferably Y is hydrogen,halogen, C₁₋₆ hydrocarbyl, or C₁₋₆ hydrocarbyloxy, and each occurrenceof R³ is independently hydrogen, C₁₋₆ hydrocarbyl, or C₁₋₆halohydrocarbyl. Still more preferably Y is hydrogen, methyl, ormethoxy, and each R³ is methyl. In some aspects, the polysiloxane blockcomprises formula (8)

wherein n has an average value of 5-80 or 10-60. In an aspect the blockcopolymer comprises poly(2,6-dimethyl-1,4-phenylene ether) blocks,poly(2,6-dimethyl-1,4-phenylene ether-co-2,3,6-trimethyl-1,4-phenyleneether) blocks or a combination thereof; polysiloxane blocks of formulacomprising, on average, 10-100 siloxane repeating units of formula (8);and terminal Z groups as described in formula (3), preferably(meth)acrylate groups. Manufacture of hydroxyl-terminated blockcopolymers are described, for example, in U.S. Pat. No. 8,722,837.

In some aspects, the poly(polyphenylene ether) copolymer is essentiallyfree of incorporated diphenoquinone residues. In this context,“essentially free” means that the less than 1 wt % (wt %) ofpoly(polyphenylene ether) molecules comprise the residue of adiphenoquinone. As described in U.S. Pat. No. 3,306,874 to Hay,synthesis of poly(polyphenylene ether) by oxidative polymerization ofmonohydric phenol yields not only the desired poly(polyphenylene ether)but also a diphenoquinone as side product. For example, when themonohydric phenol is 2,6-dimethylphenol,3,3′,5,5′-tetramethyldiphenoquinone is generated. Typically, thediphenoquinone is “reequilibrated” into the poly(polyphenylene ether)(i.e., the diphenoquinone is incorporated into the poly(polyphenyleneether) structure) by heating the polymerization reaction mixture toyield a poly(polyphenylene ether) comprising terminal or internaldiphenoquinone residues. For example, when a poly(polyphenylene ether)is prepared by oxidative polymerization of 2,6-dimethylphenol to yieldpoly(2,6-dimethyl-1,4-phenylene ether) and3,3′,5,5′-tetramethyldiphenoquinone, reequilibration of the reactionmixture can produce a poly(polyphenylene ether) with terminal andinternal residues of incorporated diphenoquinone. However, suchreequilibration reduces the molecular weight of the poly(polyphenyleneether). Accordingly, when a higher molecular weight poly(polyphenyleneether) is desired, it can be desirable to separate the diphenoquinonefrom the poly(polyphenylene ether) rather than reequilibrating thediphenoquinone into the poly(polyphenylene ether) chains. Such aseparation can be achieved, for example, by precipitation of thepoly(polyphenylene ether) in a solvent or solvent mixture in which thepoly(polyphenylene ether) is insoluble and the diphenoquinone issoluble. For example, when a poly(polyphenylene ether) is prepared byoxidative polymerization of 2,6-dimethylphenol in toluene to yield atoluene solution comprising poly(2,6-dimethyl-1,4-phenylene ether) and3,3′,5,5′-tetramethyldiphenoquinone, a poly(2,6-dimethyl-1,4-phenyleneether) essentially free of diphenoquinone can be obtained by mixing 1volume of the toluene solution with 1-4 volumes of methanol or amethanol/water mixture. Alternatively, the amount of diphenoquinoneside-product generated during oxidative polymerization can be minimized(e.g., by initiating oxidative polymerization in the presence of lessthan 10 wt % of the monohydric phenol and adding at least 95 wt % of themonohydric phenol over the course of at least 50 minutes), and/or thereequilibration of the diphenoquinone into the poly(polyphenylene ether)chain can be minimized (e.g., by isolating the poly(polyphenylene ether)no more than 200 minutes after termination of oxidative polymerization).These approaches are described in International Patent ApplicationPublication No. WO2009/104107 A1 of Delsman et al. In an alternativeapproach using the temperature-dependent solubility of diphenoquinone intoluene, a toluene solution containing diphenoquinone andpoly(polyphenylene ether) can be adjusted to a temperature of 25° C., atwhich diphenoquinone is poorly soluble but the poly(polyphenylene ether)is soluble, and the insoluble diphenoquinone can be removed bysolid-liquid separation (e.g., filtration).

The poly(polyphenylene ether) copolymers useful herein are lowermolecular weight poly(polyphenylene ether) copolymers. Thepoly(polyphenylene ether) copolymer can have a number average molecularweight of 500-7,000 grams per mole (g/mol), and a weight averagemolecular weight of 500-15,000 g/mol, as determined by gel permeationchromatography using polystyrene standards. In some aspects, the numberaverage molecular weight can be 750-4,000 g/mol, and the weight averagemolecular weight can be 1,500-9,000 g/mol, as determined by gelpermeation chromatography using polystyrene standards.

In some aspects, the poly(polyphenylene ether) copolymer has anintrinsic viscosity of 0.03-1 deciliter per gram. For example, thepoly(polyphenylene ether) can have an intrinsic viscosity of 0.25-1deciliter per gram (dl/g), or 0.25-0.7 dl/g, or 0.35-0.55 dl/g,0.35-0.50 dl/g, each measured at 25° C. in chloroform using an Ubbelohdeviscometer. In other aspects, the poly(polyphenylene ether) copolymercan have an intrinsic viscosity of 0.03-0.13 dl/g, or 0.05-0.1 dl/g, or0.1-0.15 dl/g, measured at 25° C. in chloroform using an Ubbelohdeviscometer. The poly(phenylene ether)-polysiloxane block copolymer canhave an intrinsic viscosity of at least 0.1 dl/g, as measured byUbbelohde viscometer at 25° C. in chloroform. In some aspects, theintrinsic viscosity is 0.1-0.5 dl/g.

A method for preparing the poly(polyphenylene ether) copolymers caninclude a cycloaddition reaction followed by oxidative polymerization.The cycloaddition reaction includes reacting a cycloaddition monomerprecursor comprising an alkene or an alkyne with a conjugated diene viaa cycloaddition reaction to provide a cycloaddition monomer product,wherein the cycloaddition monomer precursor comprises a monohydricphenol, a dihydric phenol, a bisphenol, or a combination thereof. Insome aspects, the alkene or an alkyne of the cycloaddition monomerprecursor is terminal alkene or alkyne. The alkene or alkyne group canundergo cycloaddition reaction, such as a [4+2] cycloaddition (e.g.,Diels-Alder reaction), with the conjugated diene to provide a monomerhaving an unsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl)group (i.e., the cycloaddition monomer product). After thecycloaddition, the cycloaddition monomer product can then undergooxidative polymerization with an unsubstituted or substituted monohydricphenol, a dihydric phenol, a bisphenol, or a combination thereof toprovide a hydroxyl-terminated poly(phenylene ether) copolymer having anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group.The hydroxyl-terminated poly(phenylene ether) copolymer having anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant groupcan be reacted with a compound to provide a poly(phenylene ether)copolymer having at least one terminal functional group and anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group.

A method for preparing the poly(phenylene ether) copolymers can includeoxidative polymerization followed by cycloaddition. Oxidativepolymerization of a polymerization precursor comprising an alkene oralkyne substituent with a monohydric phenol, a dihydric phenol, abisphenol, or a combination thereof can provide a hydroxyl-terminatedpolymerized intermediate, wherein the polymerization precursor comprisesa monohydric phenol, a dihydric phenol, a bisphenol, or a combinationthereof. The alkene and/or alkyne groups of the polymerized intermediatecan then undergo a cycloaddition reaction with a conjugated diene toprovide a hydroxyl-terminated poly(phenylene ether) copolymer having anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group.The alkene and/or the alkyne groups of the polymerized intermediate canbe an unsubstituted or substituted C₃₋₆alkenyl group, aC₅-C₆cycloalkenyl group, a C₃₋₆alkynyl group, or a combination thereof.In some aspects, the alkene and/or the alkyne groups of the polymerizedintermediate are terminal alkene and/or alkyne groups. At least one ofthe hydroxyl groups of the hydroxyl-terminated poly(phenylene ether)copolymer can be reacted with a compound to provide poly(phenyleneether) copolymer having at least one terminal functional group and anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group.

The conjugated diene used in the cycloaddition reaction of the foregoingmethods can be any conjugated s-cis diene known in the art or a dienecapable of forming a conjugated s-cis diene (e.g., when exposed to heat,light, or acid). In some aspects, the diene is an unsubstituted orsubstituted 1,3-cyclopentadiene, an unsubstituted or substituted1,3-cyclohexadiene, or an unsubstituted or substituted conjugatedterpene. As used herein, the term “terpene” is a compound derived fromisopentyl pyrophosphate or dimethylallyl pyrophosphate, encompassinghemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes,triterpenes, tetraterpenes and polyterpenes. The term “conjugatedterpene” as used herein refers to a compound that includes at least oneconjugated diene, for example two double bonds joined by a single bond.In order to react in a cycloaddition reaction, the conjugated terpeneshould be capable of forming an s-cis configuration. Therefore, theconjugated terpene may be s-cis or s-trans, as long as it is capableforming a conjugated s-cis diene. Non-limiting examples of conjugatedterpenes include isoprene, myrcene, α-ocimene, β-ocimene, α-farnesene,β-farnesene, β-springene, geranylfarnesene, neophytadiene,cis-phyta-1,3-diene, trans-phyta-1,3-diene, isodehydrosqualene,isosqualane, and the like.

The oxidative polymerization step of the foregoing methods can becarried out in the presence of a polymerization catalyst comprising acatalyst metal ion and a catalyst amine ligand, oxygen, and solvent. Thepolymerization catalyst can be prepared in situ by mixing the catalystmetal ion and the catalyst amine ligand. The solvent can be benzene,toluene, xylenes, mesitylene, chlorobenzene, dichlorobenzenes,chloroform, or combinations thereof. In some aspects, the solventcomprises toluene. The molecular oxygen can be provided, for example, ina purified form or as air. Derivatization of one or both of the terminalhydroxyl groups to provide terminal functional groups can be by methodsknown in the art.

The poly(phenylene ether) copolymers of the present disclosure can bereactive components in curable compositions. The curable composition ancomprise a poly(phenylene ether) copolymer comprising at least oneterminal functional group and a curing promoter.

In some aspects, the curable composition can further include anauxiliary curable resin, a curable unsaturated monomer composition, orboth. The auxiliary curable resin can be a thermoset resin, for example,an epoxy resin, a cyanate ester resin, a maleimide resin, a benzoxazineresin, a vinylbenzyl ether resin, an arylcyclobutene resin, aperfluorovinyl ether resin, oligomers or polymers with curable vinylfunctionality, or a combination thereof.

Epoxy resins useful as auxiliary curable resins can be produced byreaction of phenols or polyphenols with epichlorohydrin to formpolyglycidyl ethers. Examples of useful phenols for production of epoxyresins include substituted bisphenol A, bisphenol F, hydroquinone,resorcinol, tris-(4-hydroxyphenyl)methane, and novolac resins derivedfrom phenol or o-cresol. Epoxy resins can also be produced by reactionof aromatic amines, such as p-aminophenol or methylenedianiline, withepichlorohydrin to form polyglycidyl amines. Epoxy resins can beconverted into solid, infusible, and insoluble three dimensionalnetworks by curing with cross-linkers, often called curing agents, orhardeners. Curing agents are either catalytic or coreactive. Coreactivecuring agents have active hydrogen atoms that can react with epoxygroups of the epoxy resin to form a cross-linked resin. The activehydrogen atoms can be present in functional groups comprising primary orsecondary amines, phenols, thiols, carboxylic acids, or carboxylic acidanhydrides. Examples of coreactive curing agents for epoxy resinsinclude aliphatic and cycloaliphatic amines and amine-functional adductswith epoxy resins, Mannich bases, aromatic amines, polyamides,amidoamines, phenalkamines, dicyandiamide, polycarboxylicacid-functional polyesters, carboxylic acid anhydrides,amine-formaldehyde resins, phenol-formaldehyde resins, polysulfides,polymercaptans, or a combination thereof coreactive curing agents. Acatalytic curing agent functions as an initiator for epoxy resinhomopolymerization or as an accelerator for coreactive curing agents.Examples of catalytic curing agents include tertiary amines, such as2-ethyl-4-methylimidazole, Lewis acids, such as boron trifluoride, andlatent cationic cure catalysts, such as diaryliodonium salts.

The auxiliary curable resin can be a cyanate ester. Cyanate esters arecompounds having a cyanate group (—O—C≡N) bonded to carbon via theoxygen atom, i.e. compounds with C—O—C≡N groups. Cyanate esters usefulas auxiliary curable resins can be produced by reaction of a cyanogenhalide with a phenol or substituted phenol. Examples of useful phenolsinclude bisphenols utilized in the production of epoxy resins, such asbisphenol A, bisphenol F, and novolac resins based on phenol oro-cresol. Cyanate ester prepolymers are prepared bypolymerization/cyclotrimerization of cyanate esters. Prepolymersprepared from cyanate esters and diamines can also be used.

The auxiliary curable resin can be a bismaleimide resin. Bismaleimideresins can be produced by reaction of a monomeric bismaleimide with anucleophile such as a diamine, aminophenol, or amino benzhydrazide, orby reaction of a bismaleimide with diallyl bisphenol A. Non-limitingexamples of bismaleimide resins can include 1,2-bismaleimidoethane,1,6-bismaleimidohexane, 1,3-bismaleimidobenzene,1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene,4,4′-bismaleimidodiphenylmethane, 4,4′-bismaleimidodiphenylether,3,3′-bismaleimidodiphenylsulfone, 4,4′-bismaleimidodiphenylsulfone,4,4′-bismaleimidodicyclohexylmethane,3,5-bis(4-maleimidophenyl)pyridine, 2,6-bismaleimidopyridine,1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene,1,1-bis(4-maleimidophenyl)cyclohexane,1,3-bis(dichloromaleimido)benzene,4,4′-bis(citraconimido)diphenylmethane,2,2-bis(4-maleimidophenyl)propane,1-phenyl-1,1-bis(4-maleimidophenyl)ethane,N,N-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-1,2,4-triazoleN,N′-ethylenebismaleimide, N,N′-hexamethylenebismaleimide,N,N′-m-phenylenebismaleimide, N,N′-p-phenylenebismaleimide,N,N′-4,4′-diphenylmethanebismaleimide,N,N′-4,4′-diphenyletherbismaleimide,N,N′-4,4′-diphenylsufonebismaleimide,N,N′-4,4′-dicyclohexylmethanebismaleimide,N,N′-.alpha,alpha′-4,4′-dimethylenecyclohexanebismaleimide,N,N′-m-methaxylenebismaleimide,N,N′-4,4′-diphenylcyclohexanebismaleimide, andN,N′-methylenebis(3-chloro-p-phenylene)bismaleimide, as well as themaleimide resins disclosed in U.S. Pat. No. 3,562,223 to Bargain et al.,and U.S. Pat. Nos. 4,211,860 and 4,211,861 to Stenzenberger.Bismaleimide resins can be prepared by methods known in the art, asdescribed, for example, in U.S. Pat. No. 3,018,290 to Sauters et al. Insome aspects, the bismaleimide resin is N,N′-4,4′-diphenylmethanebismaleimide.

The auxiliary curable resin can be a benzoxazine resin. As is wellknown, benzoxazine monomers are made from the reaction of threereactants, aldehydes, phenols, and primary amines with or withoutsolvent. U.S. Pat. No. 5,543,516 to Ishida describes a solvent-freemethod of forming benzoxazine monomers. An article by Ning and Ishida inJournal of Polymer Science, Chemistry Edition, vol. 32, page 1121 (1994)describes a procedure using a solvent. The procedure using solvent isgenerally common to the literature of benzoxazine monomers.

The preferred phenolic compounds for forming benzoxazines includephenols and polyphenols. The use of polyphenols with two or morehydroxyl groups reactive in forming benzoxazines can result in branchedor crosslinked products. The groups connecting the phenolic groups intoa phenol can be branch points or connecting groups in thepolybenzoxazine.

Exemplary phenols for use in the preparation of benzoxazine monomersinclude phenol, cresol, resorcinol, catechol, hydroquinone,2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene,2,7-dihydrooxynapthalene, 2-(diphenylphosphoryl)hydroquinone,2,2′-biphenol, 4,4-biphenol, 4,4′-isopropylidenediphenol (bisphenol A),4,4′-isopropylidenebis(2-methylphenol),4,4′-isopropylidenebis(2-allylphenol),4,4′(1,3-phenylenediisopropylidene)bisphenol (bisphenol M),4,4′-isopropylidenebis(3-phenylphenol)4,4′-(1,4-phenylenediisoproylidene)bisphenol (bisphenol P),4,4′-ethylidenediphenol (bisphenol E), 4,4′oxydiphenol,4,4′thiodiphenol, 4,4′-sufonyldiphenol, 4,4′ sulfinyldiphenol,4,4′-hexafluoroisoproylidene)bisphenol (Bisphenol AF),4,4′(1-phenylethylidene)bisphenol (Bisphenol AP),bis(4-hydroxyphenyl)-2,2-dichloroethylene (Bisphenol C),Bis(4-hydroxyphenyl)methane (Bisphenol-F),4,4′-(cyclopentylidene)diphenol, 4,4′-(cyclohexylidene)diphenol(Bisphenol Z), 4,4′-(cyclododecylidene)diphenol4,4′-(bicyclo[2.2.1]heptylidene)diphenol,4,4′-(9H-fluorene-9,9-diyl)diphenol, isopropylidenebis(2-allylphenol),3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one,1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol,3,3,3′,3′-tetramethyl-2,2′,3,3′-tetrahydro-1,1′-spirobi[indene]-5,6′-diol(Spirobiindane), dihydroxybenzophenone (bisphenol K),tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane,tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane,tris(3-methyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethanedicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienylbis(ortho-cresol), dicyclopentadienyl bisphenol, and the like.

The aldehyde used to form the benzoxazine can be any aldehyde. In someaspects, the aldehyde has 1-10 carbon atoms. In some aspects, thealdehyde is formaldehyde. The amine used to form the benzoxazine can bean aromatic amine, an aliphatic amine, an alkyl substituted aromatic, oran aromatic substituted alkyl amine. The amine can also be a polyamine,although the use of polyamines will, under some circumstances, yieldpolyfunctional benzoxazine monomers. Polyfunctional benzoxazine monomersare more likely to result in branched and/or crosslinkedpolybenzoxazines than monofunctional benzoxazines, which would beanticipated to yield thermoplastic polybenzoxazines.

The amines for forming benzoxazines generally have 1-40 carbon atomsunless they include aromatic rings, and then they can have 6-40 carbonatoms. The amine of di- or polyfunctional can also serve as a branchpoint to connect one polybenzoxazine to another. Thermal polymerizationhas been the preferred method for polymerizing benzoxazine monomers. Thetemperature to induce thermal polymerization is typically varied from150-300° C. The polymerization is typically done in bulk, but could bedone from solution or otherwise. Catalysts, such as carboxylic acids,have been known to slightly lower the polymerization temperature oraccelerate the polymerization rate at the same temperature.

The auxiliary curable resin can be a vinylbenzyl ether resin. Vinylbenzyl ether resins can be readily prepared from condensation of aphenol with a vinyl benzyl halide, such as vinylbenzyl chloride toproduce a vinylbenzyl ether. Bisphenol-A and trisphenols and polyphenolsare generally used to produce poly(vinylbenzyl ethers) which can be usedto produce crosslinked thermosetting resins. Vinyl benzyl ethers usefulin the present composition can include those vinylbenzyl ethers producedfrom reaction of vinylbenzyl chloride or vinylbenzyl bromide withresorcinol, catechol, hydroquinone, 2,6-dihydroxy naphthalene,2,7-dihydroxynapthalene, 2-(diphenylphosphoryl)hydroquinone,bis(2,6-dimethylphenol) 2,2′-biphenol, 4,4-biphenol,2,2′,6,6′-tetramethylbiphenol, 2,2′,3,3′,6,6′-hexamethylbiphenol,3,3′,5,5′-tetrabromo-2,2′6,6′-tetramethylbiphenol,3,3′-dibromo-2,2′,6,6′-tetramethylbiphenol,2,2′,6,6′-tetramethyl-3,3′5-dibromobiphenol, 4,4′-isopropylidenediphenol(bisphenol A), 4,4′-isopropylidenebis(2,6-dibromophenol)(tetrabromobisphenol A), 4,4′-isopropylidenebis(2,6-dimethylphenol)(teramethylbisphenol A), 4,4′-isopropylidenebis(2-methylphenol),4,4′-isopropylidenebis(2-allylphenol),4,4′(1,3-phenylenediisopropylidene)bisphenol (bisphenol M),4,4′-isopropylidenebis(3-phenylphenol)4,4′-(1,4-phenylenediisoproylidene)bisphenol (bisphenol P),4,4′-ethylidenediphenol (bisphenol E), 4,4′oxydiphenol,4,4′thiodiphenol, 4,4′thiobis(2,6-dimethylphenol), 4,4′-sufonyldiphenol,4,4′-sufonylbis(2,6-dimethylphenol) 4,4′ sulfonyldiphenol,4,4′-hexafluoroisoproylidene)bisphenol (Bisphenol AF),4,4′(1-phenylethylidene)bisphenol (Bisphenol AP),bis(4-hydroxyphenyl)-2,2-dichloroethylene (Bisphenol C),bis(4-hydroxyphenyl)methane (Bisphenol-F), bis(2,6-dimethylhydroxyphenyl)methane, 4,4′-(cyclopentylidene)diphenol,4,4′-(cyclohexylidene)diphenol (Bisphenol Z),4,4′-(cyclododecylidene)diphenol4,4′-(bicyclo[2.2.1]heptylidene)diphenol,4,4′-(9H-fluorene-9,9-diyl)diphenol,3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one,1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol,1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol,3,3,3′,3′-tetramethyl-2,2′,3,3′-tetrahydro-1,1′-spirobi[indene]-5,6′-diol(Spirobiindane), dihydroxybenzophenone (bisphenol K),tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane,tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane,tris(3-methyl-4-hydroxyphenyl)methane,tris(3,5-dimethyl-4-hydroxyphenyl)methane,tetrakis(4-hydroxyphenyl)ethane,tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane,bis(4-hydroxyphenyl)phenylphosphine oxide,dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienylbis(ortho-cresol), dicyclopentadienyl bisphenol, and the like.

The auxiliary curable resin can be an arylcyclobutene resin.Arylcyclobutenes include those derived from compounds of the generalstructure

wherein B is an organic or inorganic radical of valence n (includingcarbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl,arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene,diarylmethylidene, methylidene dialkylsilanyl, arylalkylsilanyl,diarylsilanyl and C₆₋₂₀ phenolic compounds); each occurrence of X isindependently hydroxy or C₁₋₂₄ hydrocarbyl (including linear andbranched alkyl and cycloalkyl); and each occurrence of Z isindependently hydrogen, halogen, or C₁₋₁₂ hydrocarbyl; and n is 1-1000,or 1-8, or 2, 3, or 4. Other useful arylcyclobutenes and methods ofarylcyclobutene synthesis can be found in U.S. Pat. Nos. 4,743,399,4,540,763, 4,642,329, 4,661,193, and 4,724,260 to Kirchhoff et al., andU.S. Pat. No. 5,391,650 to Brennan et al.

The auxiliary curable resin can be a perfluorovinyl ether resin.Perfluorovinyl ethers are typically synthesized from phenols andbromotetrafluoroethane followed by zinc catalyzed reductive eliminationproducing ZnFBr and the desired perfluorovinylether. By this route bis,tris, and other polyphenols can produce bis-, tris- andpoly(perfluorovinylether)s. Non-limiting examples of phenols useful intheir synthesis include resorcinol, catechol, hydroquinone,2,6-dihydroxy naphthalene, 2,7-dihydroxynapthalene,2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol)2,2′-biphenol, 4,4-biphenol, 2,2′,6,6′-tetramethylbiphenol,2,2′,3,3′,6,6′-hexamethylbiphenol,3,3′,5,5′-tetrabromo-2,2′6,6′-tetramethylbiphenol,3,3′-dibromo-2,2′,6,6′-tetramethylbiphenol,2,2′,6,6′-tetramethyl-3,3′5-dibromobiphenol, 4,4′-isopropylidenediphenol(bisphenol A), 4,4′-isopropylidenebis(2,6-dibromophenol)(tetrabromobisphenol A), 4,4′-isopropylidenebis(2,6-dimethylphenol)(teramethylbisphenol A), 4,4′-isopropylidenebis(2-methylphenol),4,4′-isopropylidenebis(2-allylphenol),4,4′(1,3-phenylenediisopropylidene)bisphenol (bisphenol M),4,4′-isopropylidenebis(3-phenylphenol)4,4′-(1,4-phenylenediisoproylidene)bisphenol (bisphenol P),4,4′-ethylidenediphenol (bisphenol E), 4,4′oxydiphenol,4,4′thiodiphenol, 4,4′thiobis(2,6-dimethylphenol), 4,4′-sufonyldiphenol,4,4′-sufonylbis(2,6-dimethylphenol) 4,4′ sulfinyldiphenol,4,4′-hexafluoroisoproylidene)bisphenol (Bisphenol AF),4,4′(1-phenylethylidene)bisphenol (Bisphenol AP),bis(4-hydroxyphenyl)-2,2-dichloroethylene (Bisphenol C),bis(4-hydroxyphenyl)methane (Bisphenol-F),bis(2,6-dimethyl-4-hydroxyphenyl)methane,4,4′-(cyclopentylidene)diphenol, 4,4′-(cyclohexylidene)diphenol(Bisphenol Z), 4,4′-(cyclododecylidene)diphenol4,4′-(bicyclo[2.2.1]heptylidene)diphenol,4,4′-(9H-fluorene-9,9-diyl)diphenol,3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one,1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol,1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol,3,3,3′,3′-tetramethyl-2,2′,3,3′-tetrahydro-1,1′-spirobi[indene]-5,6′-diol(Spirobiindane), dihydroxybenzophenone (bisphenol K),tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane,tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane,tris(3-methyl-4-hydroxyphenyl)methane,tris(3,5-dimethyl-4-hydroxyphenyl)methane,tetrakis(4-hydroxyphenyl)ethane,tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane,bis(4-hydroxyphenyl)phenylphosphine oxide,dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienylbis(2-methylphenol), dicyclopentadienyl bisphenol, and the like.

The curable composition can include an oligomer or polymer with curablevinyl functionality. Such materials include oligomers and polymershaving crosslinkable unsaturation. Examples include styrene butadienerubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR)having unsaturated bonding based on butadiene; natural rubber (NR),isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (a copolymerof isobutylene and isoprene, IIR), and halogenated butyl rubber havingunsaturated bonding based on isoprene; ethylene-α-olefin copolymerelastomers having unsaturated bonding based on dicyclopentadiene (DCPD),ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD) (namely,ethylene-α-olefin copolymers obtained by copolymerizing ethylene, anα-olefin, and a diene, such as ethylene-propylene-diene terpolymer(EPDM) and ethylene-butene-diene terpolymer (EBDM). In some aspects, anEBDM is used. Examples also include hydrogenated nitrile rubber,fluorocarbon rubbers such as vinylidenefluoride-hexafluoropropenecopolymer and vinylidenefluoride-pentafluoropropene copolymer,epichlorohydrin homopolymer (CO), copolymer rubber (ECO) prepared fromepichlorohydrin and ethylene oxide, epichlorohydrin allyl glycidylcopolymer, propylene oxide allyl glycidyl ether copolymer, propyleneoxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber(ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonatedpolyethylene rubber (CSM), polysulfide rubber (T) and ethylene acrylicrubber. Further examples include various liquid rubbers, for examplevarious types of liquid butadiene rubbers, and the liquid atacticbutadiene rubber that is butadiene polymer with 1,2-vinyl connectionprepared by anionic living polymerization. It is also possible to useliquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN,VTBN, ATBN, etc. by Ube Industries, Ltd.), liquid chloroprene rubber,liquid polyisoprene, dicyclopentadiene type hydrocarbon polymer, andpolynorbornene (for example, as sold by ELF ATOCHEM).

Polybutadiene resins, generally polybutadienes containing high levels of1,2 addition can be desirable in curable compositions. Examples includethe functionalized polybutadienes and poly(butadiene-styrene) randomcopolymers sold by RICON RESINS, Inc. under the trade names RICON,RICACRYL, and RICOBOND resins. These include butadienes containing bothlow vinyl content such as RICON 130, 131, 134, 142; polybutadienescontaining high vinyl content such as RICON 150, 152, 153, 154, 156,157, and P30D; random copolymers of styrene and butadiene includingRICON 100, 181, 184, and maleic anhydride grafted polybutadienes and thealcohol condensates derived therefrom such as RICON 130MA8, RICON MA13,RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20,RICON 184MA6 and RICON 156MA17. Also included are polybutadienes thatcan be used to improve adhesion including RICOBOND 1031, RICOBOND 1731,RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500; thepolybutadienes RICON 104 (25% polybutadiene in heptane), RICON 257 (35%polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene);(meth)acrylic functionalized polybutadienes such as polybutadienediacrylates and polybutadiene dimethacrylates. These materials are soldunder the tradenames RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801.Also are included are powder dispersions of functional polybutadienederivatives including, for example, RICON 150D, 152D, 153D, 154D, P30D,RICOBOND 0 1731 HS, and RICOBOND 1756HS. Further butadiene resinsinclude poly(butadiene-isoprene) block and random copolymers, such asthose with molecular weights from 3,000-50,000 grams per mole andpolybutadiene homopolymers having molecular weights from 3,000-50,000grams per mole. Also included are polybutadiene, polyisoprene, andpolybutadiene-isoprene copolymers functionalized with maleic anhydridefunctions, 2-hydroxyethylmaleic functions, or hydroxylatedfunctionality.

Further examples of oligomers and polymers with curable vinylfunctionality include unsaturated polyester resins based on maleicanhydride, fumaric acid, itaconic acid and citraconic acid; unsaturatedepoxy (meth)acrylate resins containing acryloyl groups, or methacryloylgroup; unsaturated epoxy resins containing vinyl or allyl groups,urethane (meth)acrylate resin, polyether (meth)acrylate resin,polyalcohol (meth)acrylate resins, alkyd acrylate resin, polyesteracrylate resin, spiroacetal acrylate resin, diallyl phthalate resin,diallyl tetrabromophthalate resin, diethyleneglycol bisallylcarbonateresin, and polyethylene polythiol resin.

In some aspects, the curable composition comprises a curable unsaturatedmonomer composition. The curable unsaturated monomer composition caninclude, for example, a monofunctional styrenic compound (e.g.,styrene), a monofunctional (meth)acrylic compound, a polyfunctionalallylic compound, a polyfunctional (meth)acrylate, a polyfunctional(meth)acrylamide, a polyfunctional styrenic compound, or a combinationthereof. For example, in some aspects, the curable unsaturated monomercomposition can be an alkene-containing monomer or an alkyne-containingmonomer. Exemplary alkene- and alkyne-containing monomers include thosedescribed in U.S. Pat. No. 6,627,704 to Yeager et al. Non-limitingexamples of alkene-containing monomers include acrylate, methacrylate,and vinyl ester functionalized materials capable of undergoing freeradical polymerization. Of particular use are acrylate and methacrylatematerials. They can be monomers and/or oligomers such as(meth)acrylates, (meth)acrylamides, N-vinylpyrrolidone andvinylazlactones as disclosed in U.S. Pat. No. 4,304,705 of Heilman etal. Such monomers include mono-, di-, and polyacrylates andmethacrylates, such as methyl acrylate, methyl methacrylate, ethylacrylate, isopropyl methacrylate, isooctyl acrylate, isobornyl acrylate,isobornyl methacrylate, acrylic acid, n-hexyl acrylate,tetrahydrofurfuryl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone,acrylonitrile, stearyl acrylate, allyl acrylate, glycerol diacrylate,glycerol triacrylate, ethylene glycol diacrylate, diethylene glycoldiacrylate, triethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate,trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate,2-phenoxyethyl acrylate, 1,4-cyclohexanediol diacrylate, pentaerythritoltriacrylate, pentaerythritol tetraacrylate, pentaerythritoltetramethacrylate, sorbitol hexaacrylate, bis[1-(2-acryloxy)]-p-ethoxyphenyldimethylmethane,2,2-bis[1-(3-acryloxy-2-hydroxy)]propoxyphenylpropane,tris(hydroxyethyl)isocyanurate trimethacrylate; the bis-acrylates andbis-methacrylates of polyethylene glycols of molecular weight average200-500 grams per mole, bis-acrylates and bis-methacrylates ofpolybutadienes of molecular weight average 1000-10,000 grams per mole,copolymerizable mixtures of acrylated monomers such as those disclosedin U.S. Pat. No. 4,652,274 to Boettcher et al. and acrylated oligomerssuch as those disclosed in U.S. Pat. No. 4,642,126 to Zador et al.

It can be desirable to crosslink the alkene- or alkyne-containingmonomer. Particularly useful as crosslinker compounds are acrylates suchas allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethyleneglycol diacrylate, diethylene glycol diacrylate, triethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol diacrylate,1, 3-propanediol dimethacrylate, trimethylolpropane triacrylate,1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,pentaerythritol tetramethacrylate, sorbitol hexaacrylate,bis[1-(2-acryloxy)]-p-ethoxyphenyldi-methylmethane,2,2-bis[1-(3-acryloxy-2-hydroxy)]propoxyphenylpropane,tris(hydroxyethyl)isocyanurate trimethacrylate; and the bis-acrylatesand bis-methacrylates of polyethylene glycols of average molecularweight 200-500 grams per mole.

Also included are allylic resins and styrenic resins for exampletriallylisocyanurate and trimethallylisocyanurate,trimethallylcyanurate, triallylcyanurate, divinyl benzene anddibromostyrene and others described in U.S. Pat. No. 6,627,704 to Yeageret al.

A curing promoter can be selected based on the functional group presenton the poly(phenylene ether) copolymer and, when present, the auxiliarycurable resin or the curable unsaturated monomer composition. Forexample, the curing promoter can comprise an amine, a dicyandiamide, apolyamide, an amidoamine, a Mannich base, an anhydride, aphenol-formaldehyde resin, a carboxylic acid functional polyester, apolysulfide, a polymercaptan, an isocyanate, a cyanate ester, or acombination thereof.

In addition to the poly(phenylene ether) copolymer, the curing promoter,and, when present, the auxiliary resin or unsaturated monomercomposition, the curable composition can, optionally, comprise asolvent. The solvent can have an atmospheric boiling point of 50 to 250°C. A boiling point in this range facilitates removal of solvent from thecurable composition while minimizing or eliminating the effects ofbubbling during solvent removal.

The solvent can be, for example, a C₃₋₈ ketone, a C₃₋₈N,N-dialkylamide,a C₄₋₁₆ dialkyl ether, a C₆₋₁₂ aromatic hydrocarbon, a C₁₋₃ chlorinatedhydrocarbon, a C₃₋₆ alkyl alkanoate, a C₂₋₆ alkyl cyanide, or acombination thereof. The carbon number ranges refer to the total numberof carbon atoms in the solvent molecule. For example, a C₄₋₁₆ dialkylether has 4 to 16 total carbon atoms, and the two alkyl groups can bethe same or different. As other examples, the 3-8 carbon atoms in the“N,N-dialkylamide” include the carbon atom in the amide group, and the2-6 carbons in the “C₂₋₆ alkyl cyanides” include the carbon atom in thecyanide group. Specific ketone solvents include, for example, acetone,methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof.Specific C₄₋₈ N,N-dialkylamide solvents include, for example,dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or acombination thereof. Specific dialkyl ether solvents include, forexample, tetrahydrofuran, ethylene glycol monomethylether, dioxane, or acombination thereof. In some aspects, the C₄₋₁₆ dialkyl ethers includecyclic ethers such as tetrahydrofuran and dioxane. In some aspects, theC₄₋₁₆ dialkyl ethers are noncyclic. The dialkyl ether can, optionally,further include one or more ether oxygen atoms within the alkyl groupsand one or more hydroxy group substituents on the alkyl groups. Thearomatic hydrocarbon solvent can comprise an ethylenically unsaturatedsolvent. Exemplary aromatic hydrocarbon solvents include, for example,benzene, toluene, xylenes, styrene, divinylbenzenes, or a combinationthereof. The aromatic hydrocarbon solvent is preferably non-halogenated.As used herein, the term “non-halogenated” means that the solvent doesnot include any fluorine, chlorine, bromine, or iodine atoms. SpecificC₃₋₆ alkyl alkanoates include, for example, methyl acetate, ethylacetate, methyl propionate, ethyl propionate, or a combination thereof.Specific C₂₋₆ alkyl cyanides include, for example, acetonitrile,propionitrile, butyronitrile, or a combination thereof. In some aspects,the solvent is acetone. In some aspects, the solvent is methyl ethylketone. In some aspects, the solvent is methyl isobutyl ketone. In someaspects, the solvent is N-methyl-2-pyrrolidone. In some aspects, thesolvent is dimethylformamide. In some aspects, the solvent is ethyleneglycol monomethyl ether.

When a solvent is utilized, the curable composition can comprise 2-100parts by weight of the solvent, based on 100 parts by weight total ofthe poly(phenylene ether) copolymer, the curing promoter, and theauxiliary resin or unsaturated monomer composition (when present). Forexample, the solvent amount can be 5-80 parts by weight, or 10-60 partsby weight, or 20-40 parts by weight, based on 100 parts by weight totalof the poly(phenylene ether) copolymer, the curing promoter, and anyauxiliary resin. The solvent can be chosen, in part, to adjust theviscosity of the curable composition. Thus, the solvent amount candepend on variables including the type and amount of poly(phenyleneether) copolymer, the type and amount of curing promoter, the type andamount of auxiliary resin, and the processing temperature used for anysubsequent processing of the curable composition, for example,impregnation of a reinforcing structure with the curable composition forthe preparation of a composite.

The curable composition can further comprise an inorganic filler.Exemplary inorganic fillers include, for example, alumina, silica(including fused silica and crystalline silica), boron nitride(including spherical boron nitride), aluminum nitride, silicon nitride,magnesia, magnesium silicate, glass fibers, glass mat, or a combinationthereof. Exemplary glass fibers include those based on E, A, C, ECR, R,S, D, and NE glasses, as well as quartz. The glass fiber can have adiameter of 2-30 micrometers (μm), or 5-25 μm, or 5-15 μm. The length ofthe glass fibers before compounding can be 2-7 millimeters (mm), or1.5-5 mm. Alternatively, longer glass fibers or continuous glass fiberscan be used. The glass fiber can, optionally, include an adhesionpromoter to improve its compatibility with the poly(phenylene ether)copolymer, the auxiliary epoxy resin, or both. Adhesion promotersinclude chromium complexes, silanes, titanates, zircon-aluminates,propylene maleic anhydride copolymers, reactive cellulose esters, andthe like. Exemplary glass fiber is commercially available from suppliersincluding, for example, OWENS CORNING, NIPPON ELECTRIC GLASS, PPG, andJOHNS MANVILLE.

When an inorganic filler is utilized, the curable composition cancomprise 2-900 parts by weight of inorganic filler, based on 100 partsby weight total of the poly(phenylene ether) copolymer, the curingpromoter, and the auxiliary curable resin. In some aspects, the curablecomposition comprises 100-900 parts by weight inorganic filler, or200-800 parts by weight inorganic filler, or 300-700 parts by weightinorganic filler, based on 100 parts by weight total poly(phenyleneether) copolymer, curing promoter, and auxiliary curable resin. In someaspects, the curable composition comprises less than 50 parts by weightinorganic filler, or less than 30 parts by weight inorganic filler, orless than 10 parts by weight inorganic filler, based of 100 parts byweight total of the poly(phenylene ether) copolymer, the curingpromoter, and the auxiliary curable resin. In some aspects, the curablecomposition can be substantially free of inorganic filler (that is, thecomposition can comprises less than 0.1 wt % of added inorganic filler,based 100 parts by weight of the poly(phenylene ether) copolymer, thecuring promoter, and the auxiliary curable resin).

The curable composition also can include a coupling agent, for example asilane coupling agent. Exemplary silane coupling agents can includebis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl) disulfide,bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxy silylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide,3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy silane,2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane,3-mercaptopropyldimethoxymethylsilane, and the like, and combinationsthereof.

The curable composition can, optionally, further comprise one or moreadditives. Exemplary additives include, for example, solvents, dyes,pigments, colorants, antioxidants, heat stabilizers, light stabilizers,plasticizers, lubricants, flow modifiers, drip retardants, flameretardants, antiblocking agents, antistatic agents, flow-promotingagents, processing aids, substrate adhesion agents, mold release agents,toughening agents, low-profile additives, stress-relief additives, or acombination thereof.

The curable composition can comprise the poly(phenylene ether) copolymerdescribed herein, a curing promoter, a solvent, and an auxiliary resin,a curable unsaturated monomer compositions, or a combination thereof. Insome aspects, an auxiliary curable resin and/or a curable unsaturatedmonomer composition is absent.

The curable composition can comprise 1-99 wt % of the auxiliary curableresin, a curable unsaturated monomer composition, or both and 1-99 wt %of the poly(phenylene ether) copolymer, each based on the total weightof the curable composition. For example, the composition can include20-99 wt % of the auxiliary curable resin, a curable unsaturated monomercomposition, or both and 1-80 wt % of the poly(phenylene ether)copolymer.

The curable composition can comprise a poly(phenylene ether) having atleast one terminal group comprising a cyanate ester, a glycidyl ether,an anhydride, an aniline, a maleimide, an activated ester, or acombination thereof; an auxiliary resin comprising cyanate ester resin,epoxy resin, bismaleimide resin, or a combination thereof; a curingpromoter; polymerization catalyst, flame retardant, filler (preferablysilica), silane coupling agent, antioxidants and other additives (heatstabilizers, antistatic agent, UV absorbent, lubricant, colorant).

While the curable composition of the present invention will over timeprovide a thermoset at ambient conditions, optimum results are achievedby the application of heating and/or the use of a free radical curingagent. The curable composition can be cured by an energetic free radicalgenerator such as ultraviolet light, electron beam or gamma radiation,or by one or more chemical free radical generators such as azo compoundsand peroxides. The composition can be ultraviolet light-cured if one ormore photoinitiators is added prior to curing. There are no specialrestrictions on the nature of the useful photoinitiators provided theygenerate radicals by the absorption of energy.

A thermoset composition (i.e., cured composition) can be obtained byheating the curable composition defined herein for a time andtemperature sufficient to evaporate the solvent and effect curing. Forexample, the curable composition can be heated to a temperature of50-250° C. to cure the composition and provide the thermosetcomposition. In curing, a cross-linked, three-dimensional polymernetwork is formed. For certain thermoset resins, for example(meth)acrylate resins, curing can also take place by irradiation withactinic radiation at a sufficient wavelength and time. In some aspects,curing the composition can include injecting the curable compositioninto a mold, and curing the injected composition at 150-250° C. in themold.

The thermoset composition can have one or more desirable properties. Forexample, the thermoset composition can have a glass transitiontemperature of greater than or equal to 180° C., preferably greater thanor equal to 190° C., more preferably greater than or equal to 200° C.,as determined according to differential scanning calorimetry as per ASTMD3418 with a 20° C./min heating rate.

The thermoset composition can have low dielectric properties. Dielectricproperties can be measured according to IPC-TM-650-2.5.5.9 Permittivityand Loss Tangent, Parallel Plate, 1 MHz to 1.5 GHz.

The thermoset composition can have low moisture absorption. Moistureabsorption can be measured according to at 85% relative humidity, 85°C., 7 days. The thermoset composition can exhibit a water absorption ofless than or equal to 5 wt %, less than or equal to 4 wt %, less than orequal to 3 wt %, less than or equal to 2 wt %, or less than or equal to1 wt % measured after immersion in deionized water at 25° C. for 24hours.

The thermoset composition can exhibit good impact strength. In someaspects, the composition exhibits an unnotched Izod impact strength ofat least 400 joules per meter, specifically 400-600 joules per meter,more specifically 450-550 joules per meter, and still more specifically480-520 joules per meter, as measured at 23° C. with a hammer energy of2 foot-pounds in accordance with ASTM D 4812-06.

The thermoset composition described herein can also be particularly wellsuited for use in forming various articles. For example, useful articlescan be in the form of a composite, a foam, a fiber, a layer, a coating,an encapsulant, an adhesive, a sealant, a molded component, a prepreg, acasing, a laminate, a metal clad laminate, an electronic composite, astructural composite, or a combination thereof. In some aspects, thearticle can be in the form of a composite that can be used in a varietyof applications, for example printed circuit boards.

In some aspects, the article is a copper-clad laminate made from acurable composition comprising a poly(phenylene ether) having at leastone terminal function group comprising (meth)acrylate, styrene,—CH₂—(C₆H₄)—CH═CH₂, allyl, or a combination thereof; an auxiliarycurable resin comprising vinyl groups; a radical initiator, flameretardant, filler (preferably silica), silane coupling agent,antioxidants and other additives (heat stabilizers, antistatic agent, UVabsorbent, lubricant, colorant).

This disclosure further encompasses the following aspects.

Aspect 1: A poly(phenylene ether) copolymer comprising first repeatingunits comprising a C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group; secondrepeating units different from the first repeating units; a copolymer ofFormula (3); and optionally, at least one terminal functional groupcomprising (meth)acrylate, styrene, —CH₂—(C₆H₄)—CH═CH₂, allyl, cyanateester, glycidyl ether, anhydride, aniline, maleimide, an activatedester, or a combination thereof,

wherein, in the formula (3), each occurrence of Q¹ and Q² independentlycomprise halogen, unsubstituted or substituted C₁₋₁₂ primary orsecondary hydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; eachoccurrence of Q³ and Q⁴ independently comprise hydrogen, halogen,unsubstituted or substituted C₁-C₁₂ primary or secondary hydrocarbyl,C₁-C₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; x and yare each independently 0-30; optionally, at least one of Q¹ to Q⁴ isunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); L is of theformula

wherein each occurrence of R³, R⁴, R⁵, and R⁶ is independently hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; w is 0 or1; and Y is

wherein each occurrence of R⁷ is independently hydrogen or C₁₋₁₂hydrocarbyl, each occurrence of R⁸ and R⁹ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or R⁸ and R⁹ together form a C₄₋₁₂cyclohydrocarbylene with the carbon atom; or L is of the formula

wherein E is 6-100, each occurrence of R is independently anunsubstituted or substituted C₁₋₁₃ alkyl, C₁₋₁₃ alkoxy, C₃₋₆ cycloalkyl,C₃₋₆ cycloalkoxy, C₆₋₁₄ aryl, C₆₋₁₀ aryloxy, C₇₋₁₃ arylalkylene, orC₇₋₁₃ alkylarylene; each p and q are independently 0 or 1, R¹ is adivalent C₂₋₈ aliphatic group, each occurrence of M is independentlyhalogen, cyano, nitro, C₁₋₈ alkylthio, C₁₋₈ alkyl, C₁₋₈ alkoxy, C₂₋₈alkenyl, C₂₋₈ alkenyloxy, C₃₋₈ cycloalkyl, C₃₋₈ cycloalkoxy, C₆₋₁₀ aryl,C₆₋₁₀ aryloxy, C₇₋₁₂ aralkyl, C₇₋₁₂ aralkoxy, C₇₋₁₂ alkylaryl, or C₇₋₁₂alkylaryloxy, and each n is independently 0, 1, 2, 3, or 4.

Aspect 2: The poly(phenylene ether) copolymer of Aspect 1, wherein:

the first repeating units have the structure

wherein each occurrence of Z¹ comprises halogen, unsubstituted orsubstituted C₁₋₁₂ primary or secondary hydrocarbyl, C₁₋₁₂hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), orC₂₋₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms, and each occurrence of Z² comprises hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms, and atleast one of Z¹ and Z² is an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl); the second repeating units have thestructure

wherein each occurrence of Z³ independently comprises halogen,unsubstituted or substituted C₁₋₁₂ primary or secondary hydrocarbyl,C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or C₂₋₁₂ halohydrocarbyloxywherein at least two carbon atoms separate the halogen and oxygen atoms,and each occurrence of Z⁴ independently comprises hydrogen, halogen,unsubstituted or substituted C₁₋₁₂ primary or secondary hydrocarbyl,C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or C₂₋₁₂ halohydrocarbyloxywherein at least two carbon atoms separate the halogen and oxygen atoms.

Aspect 3: The poly(phenylene ether) copolymer of Aspect 1 or Aspect 2,wherein the poly(phenylene ether) copolymer comprises a copolymer ofFormula (3b)

wherein each occurrence of Q⁵ and Q⁶ is independently methyl,cyclohexyl, phenyl, di-n-butylaminomethyl, morpholinomethyl, or anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); and eachoccurrence of a and b is independently 0-20, with the proviso that thesum of a and b is at least 2.

Aspect 4: The poly(phenylene ether) copolymer of any one of thepreceding aspects, wherein the second repeating units are derived from2,6-dimethyl phenol, 2,3,6-trimethyl phenol, 2-phenyl-6-methyl phenol,2-allyl-6-methyl phenol, or a combination thereof.

Aspect 5: The poly(phenylene ether) copolymer of any one of thepreceding aspects comprising a polysiloxane block comprising: repeatingunits of the formula

wherein each occurrence of R³ is independently C₁₋₁₂ hydrocarbyl orC₁₋₁₂ halohydrocarbyl; and a terminal unit of the formula

wherein: Y is hydrogen, halogen, C₁₋₁₂ hydrocarbyl, or C₁₋₁₂hydrocarbyloxy, and each occurrence of R³ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or C₁₋₁₂ halohydrocarbyl, preferably wherein Y ishydrogen, halogen, C₁₋₆ hydrocarbyl, or C₁₋₆ hydrocarbyloxy, and eachoccurrence of R³ is independently hydrogen, C₁₋₆ hydrocarbyl, or C₁₋₆halohydrocarbyl, more preferably wherein Y is hydrogen, methyl, ormethoxy, and each R³ is methyl.

Aspect 6: The poly(phenylene ether) copolymer of any one of thepreceding aspects comprising a polysiloxane block comprising thestructure

wherein n has an average value of 5-100, or 10-80 or 10-60.

Aspect 7: The poly(phenylene ether) copolymer of any one of thepreceding aspects, wherein the C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendantgroup of the first repeating unit is a—C₁-C₃alkyl(bicyclo[2.2.1]heptene) group, a—C₁-C₃alkyl(bicyclo[2.2.1]heptadiene) group, a —C₁-C₃alkyl(cyclohexene)group, a —C₁-C₃alkyl(cyclohexadiene) group, or a —C₁-C₃alkyl(C₆₋₃₀cycloalkenyl) group, wherein the C₆₋₃₀ cycloalkenyl group is derivedfrom a terpene, each optionally substituted with a C₁₋₁₂ primary orsecondary hydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or acombination thereof.

Aspect 8: The poly(phenylene ether) copolymer of any one of thepreceding aspects, wherein the first repeating units are derived from2-CH₂(C₆₋₃₀cycloalkenyl)-6-methyl phenol,2-CH₂(C₆₋₃₀cycloalkenyl)-3,6-dimethyl phenol,3-CH₂(C₆₋₃₀cycloalkenyl)-2,6-dimethyl phenol,2-phenyl-6-CH₂(C₆₋₃₀cycloalkenyl) phenol, or a combination thereof.

Aspect 9: A method of preparing the poly(phenylene ether) copolymer ofany one of Aspects 1-8, comprising: reacting a cycloaddition monomerprecursor comprising an alkene or an alkyne with a conjugated diene viaa cycloaddition reaction to provide a cycloaddition monomer product,wherein the cycloaddition monomer precursor comprises a monohydricphenol, a dihydric phenol, a bisphenol, or a combination thereof;oxidatively polymerizing the cycloaddition monomer product with anunsubstituted or substituted monohydric phenol, a dihydric phenol, abisphenol, or a combination thereof to provide a hydroxyl-terminatedpoly(phenylene ether) copolymer having an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group; and optionally, reacting atleast one hydroxyl terminal group of the hydroxyl-terminatedpoly(phenylene ether) copolymer having an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group with a compound to providepoly(phenylene ether) copolymer having an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group and at least one terminalfunctional group.

Aspect 10: A method of preparing the poly(phenylene ether) copolymer ofany one of Aspects 1-8, comprising oxidatively polymerizing apolymerization precursor comprising an alkene or alkyne with amonohydric phenol, a dihydric phenol, a bisphenol, or a combinationthereof, to provide a hydroxyl-terminated polymerized intermediate,wherein the polymerization precursor comprises a monohydric phenol, adihydric phenol, a bisphenol, or a combination thereof; reacting thehydroxyl-terminated polymerized intermediate with a conjugated diene viaa cycloaddition reaction to provide a hydroxyl-terminated poly(phenyleneether) copolymer having an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group; and optionally, reacting atleast one hydroxyl terminal group of the hydroxyl-terminated polymerizedintermediate with a compound to provide a poly(phenylene ether)copolymer having an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group and at least one terminalfunctional group.

Aspect 11: A curable composition comprising the poly(phenylene ether)copolymer of any one of Aspects 1 to 8; and a curing promoter comprisingan amine, a dicyandiamide, a polyamide, an amidoamine, a Mannich base,an anhydride, a phenol-formaldehyde resin, a carboxylic acid functionalpolyester, a polysulfide, a polymercaptan, an isocyanate, a cyanateester, or a combination thereof.

Aspect 12: The curable composition of Aspect 11, further comprising anauxiliary curable resin comprising an epoxy resin, a cyanate esterresin, a maleimide resin, a benzoxazine resin, a vinylbenzyl etherresin, an arylcyclobutene resin, a perfluorovinyl ether resin, oligomersor polymers with curable vinyl functionality, or a combination thereof;a curable unsaturated monomer comprising a monofunctional styreniccompound, a monofunctional (meth)acrylic compound, a polyfunctionalallylic compound, a polyfunctional (meth)acrylate, a polyfunctional(meth)acrylamide, a polyfunctional styrenic compound, or a combinationthereof; or a combination thereof.

Aspect 13: A thermoset composition comprising the curable composition ofAspect 11 or Aspect 12, wherein the thermoset composition has a glasstransition temperature of greater than or equal to 180° C., preferablygreater than or equal to 190° C., more preferably greater than or equalto 200° C., as determined according to differential scanning calorimetryas per ASTM D3418 with a 20° C./min heating rate.

Aspect 14: An article comprising the thermoset composition of Aspect 13,wherein the article is a composite, a foam, a fiber, a layer, a coating,an encapsulant, an adhesive, a sealant, a molded component, a prepreg, acasing, a laminate, a metal clad laminate, an electronic composite, astructural composite, or a combination thereof.

Aspect 15: A method for the manufacture of a thermoset composition, themethod comprising curing the curable composition of Aspect 11 or Aspect12, preferably at a temperature of 50 to 250° C.

The compositions, methods, and articles can alternatively comprise,consist of, or consist essentially of, any appropriate materials, steps,or components herein disclosed. The compositions, methods, and articlescan additionally, or alternatively, be formulated so as to be devoid, orsubstantially free, of any materials (or species), steps, or components,that are otherwise not necessary to the achievement of the function orobjectives of the compositions, methods, and articles.

All ranges disclosed herein are inclusive of the endpoints, and theendpoints are independently combinable with each other (e.g., ranges of“up to 25 wt %, or, more specifically, 5 wt % to 20 wt %”, is inclusiveof the endpoints and all intermediate values of the ranges of “5 wt % to25 wt %,” etc.). “Combinations” is inclusive of blends, mixtures,alloys, reaction products, and the like. The terms “first,” “second,”and the like, do not denote any order, quantity, or importance, butrather are used to distinguish one element from another. The terms “a”and “an” and “the” do not denote a limitation of quantity and are to beconstrued to cover both the singular and the plural, unless otherwiseindicated herein or clearly contradicted by context. “Or” means “and/or”unless clearly stated otherwise. Reference throughout the specificationto “some embodiments”, “an embodiment”, and so forth, means that aparticular element described in connection with the embodiment isincluded in at least one embodiment described herein, and may or may notbe present in other embodiments. In addition, it is to be understoodthat the described elements may be combined in any suitable manner inthe various embodiments. A “combination thereof” is open and includesany combination comprising at least one of the listed components orproperties optionally together with a like or equivalent component orproperty not listed.

Unless specified to the contrary herein, all test standards are the mostrecent standard in effect as of the filing date of this application, or,if priority is claimed, the filing date of the earliest priorityapplication in which the test standard appears.

Unless defined otherwise, technical and scientific terms used hereinhave the same meaning as is commonly understood by one of skill in theart to which this application belongs. All cited patents, patentapplications, and other references are incorporated herein by referencein their entirety. However, if a term in the present applicationcontradicts or conflicts with a term in the incorporated reference, theterm from the present application takes precedence over the conflictingterm from the incorporated reference.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group.

The term “alkyl” means a branched or straight chain, unsaturatedaliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl,n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl.“Alkenyl” means a straight or branched chain, monovalent hydrocarbongroup having at least one carbon-carbon double bond (e.g., ethenyl(—HC═CH₂)). “Alkoxy” means an alkyl group that is linked via an oxygen(i.e., alkyl-O—), for example methoxy, ethoxy, and sec-butyloxy groups.“Alkylene” means a straight or branched chain, saturated, divalentaliphatic hydrocarbon group (e.g., methylene (—CH₂—) or, propylene(—(CH₂)₃—)). “Cycloalkylene” means a divalent cyclic alkylene group,—C_(n)H_(2n-x), wherein x is the number of hydrogens replaced bycyclization(s). “Cycloalkenyl” means a monovalent group having one ormore rings and one or more carbon-carbon double bonds in the ring,wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).“Aryl” means an aromatic hydrocarbon group containing the specifiednumber of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.“Arylene” means a divalent aryl group. “Alkylarylene” means an arylenegroup substituted with an alkyl group. “Arylalkylene” means an alkylenegroup substituted with an aryl group (e.g., benzyl). The prefix “halo”means a group or compound including one more of a fluoro, chloro, bromo,or iodo substituent. A combination of different halo groups (e.g., bromoand fluoro), or only chloro groups can be present. The prefix “hetero”means that the compound or group includes at least one ring member thatis a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein theheteroatom(s) is each independently N, O, S, Si, or P. “Substituted”means that the compound or group is substituted with at least one (e.g.,1, 2, 3, or 4) substituents that can each independently be a C₁₋₉alkoxy, a C₁₋₉ haloalkoxy, a nitro (—NO₂), a cyano (—CN), a C₁₋₆ alkylsulfonyl (—S(═O)₂-alkyl), a C₆₋₁₂ aryl sulfonyl (—S(═O)₂-aryl)a thiol(—SH), a thiocyano (—SCN), a tosyl (CH₃C₆H₄SO₂—), a C₃₋₁₂ cycloalkyl, aC₂₋₁₂ alkenyl, a C₅₋₁₂ cycloalkenyl, a C₆₋₁₂ aryl, a C₇₋₁₃ arylalkylene,a C₄₋₁₂ heterocycloalkyl, and a C₃₋₁₂ heteroaryl instead of hydrogen,provided that the substituted atom's normal valence is not exceeded. Thenumber of carbon atoms indicated in a group is exclusive of anysubstituents. For example —CH₂CH₂CN is a C₂ alkyl group substituted witha nitrile.

While particular embodiments have been described, alternatives,modifications, variations, improvements, and substantial equivalentsthat are or may be presently unforeseen may arise to applicants orothers skilled in the art. Accordingly, the appended claims as filed andas they may be amended are intended to embrace all such alternatives,modifications variations, improvements, and substantial equivalents.

1. A poly(phenylene ether) copolymer comprising first repeating unitscomprising a C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group; secondrepeating units different from the first repeating units; a copolymer ofFormula (3); and optionally, at least one terminal functional groupcomprising (meth)acrylate, styrene, —CH₂—(C₆H₄)—CH═CH₂, allyl, cyanateester, glycidyl ether, anhydride, aniline, maleimide, an activatedester, or a combination thereof,

wherein in Formula (3): each occurrence of Q¹ and Q² independentlycomprise halogen, unsubstituted or substituted C₁₋₁₂ primary orsecondary hydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; eachoccurrence of Q³ and Q⁴ independently comprise hydrogen, halogen,unsubstituted or substituted C₁-C₁₂ primary or secondary hydrocarbyl,C₁-C₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; x and yare each independently 0-30; optionally, at least one of Q¹ to Q⁴ isunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); L is of theformula

wherein each occurrence of R³, R⁴, R⁵, and R⁶ is independently hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; w is 0 or1; and Y is

wherein each occurrence of R⁷ is independently hydrogen or C₁₋₁₂hydrocarbyl, each occurrence of R⁸ and R⁹ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or R⁸ and R⁹ together form a C₄₋₁₂cyclohydrocarbylene with the carbon atom; or L is of the formula

wherein E is 6-100, each occurrence of R is independently anunsubstituted or substituted C₁₋₁₃ alkyl, C₁₋₁₃ alkoxy, C₃₋₆ cycloalkyl,C₃₋₆ cycloalkoxy, C₆₋₁₄ aryl, C₆₋₁₀ aryloxy, C₇₋₁₃ arylalkylene, orC₇₋₁₃ alkylarylene; each p and q are independently 0 or 1, R¹ is adivalent C₂₋₈ aliphatic group, each occurrence of M is independentlyhalogen, cyano, nitro, C₁₋₈ alkylthio, C₁₋₈ alkyl, C₁₋₈ alkoxy, C₂₋₈alkenyl, C₂₋₈ alkenyloxy, C₃₋₈ cycloalkyl, C_(3-8 cycloalkoxy, C) ₆₋₁₀aryl, C₆₋₁₀ aryloxy, C₇₋₁₂ aralkyl, C₇₋₁₂ aralkoxy, C₇₋₁₂ alkylaryl, orC₇₋₁₂ alkylaryloxy, and each n is independently 0, 1, 2, 3, or
 4. 2. Thepoly(phenylene ether) copolymer of claim 1, wherein: the first repeatingunits have the structure

wherein each occurrence of Z¹ comprises halogen, unsubstituted orsubstituted C₁₋₁₂ primary or secondary hydrocarbyl, C₁₋₁₂hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), orC₂₋₁₂ halohydrocarbyloxy wherein at least two carbon atoms separate thehalogen and oxygen atoms, and each occurrence of Z² comprises hydrogen,halogen, unsubstituted or substituted C₁₋₁₂ primary or secondaryhydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy,C₁₋₆alkyl(C₆₋₃₀cycloalkenyl), or C₂₋₁₂ halohydrocarbyloxy wherein atleast two carbon atoms separate the halogen and oxygen atoms, and atleast one of Z¹ and Z² is an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl); the second repeating units have thestructure

wherein each occurrence of Z³ independently comprises halogen,unsubstituted or substituted C₁₋₁₂ primary or secondary hydrocarbyl,C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or C₂₋₁₂ halohydrocarbyloxywherein at least two carbon atoms separate the halogen and oxygen atoms,and each occurrence of Z⁴ independently comprises hydrogen, halogen,unsubstituted or substituted C₁₋₁₂ primary or secondary hydrocarbyl,C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or C₂₋₁₂ halohydrocarbyloxywherein at least two carbon atoms separate the halogen and oxygen atoms.3. The poly(phenylene ether) copolymer of claim 1 comprising formula(3b)

wherein each occurrence of Q⁵ and Q⁶ is independently methyl,cyclohexyl, phenyl, di-n-butylaminomethyl, morpholinomethyl, or anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl); and eachoccurrence of a and b is independently 0-20, with the proviso that thesum of a and b is at least
 2. 4. The poly(phenylene ether) copolymer ofclaim 1, wherein the second repeating units are derived from2,6-dimethyl phenol, 2,3,6-trimethyl phenol, 2-phenyl-6-methyl phenol,2-allyl-6-methyl phenol, or a combination thereof.
 5. The poly(phenyleneether) copolymer of claim 1 comprising a polysiloxane block comprising:repeating units of the formula

wherein each occurrence of R³ is independently C₁₋₁₂ hydrocarbyl orC₁₋₁₂ halohydrocarbyl; and a terminal unit of the formula

wherein: Y is hydrogen, halogen, C₁₋₁₂ hydrocarbyl, or C₁₋₁₂hydrocarbyloxy, and each occurrence of R³ is independently hydrogen,C₁₋₁₂ hydrocarbyl, or C₁₋₁₂ halohydrocarbyl.
 6. The poly(phenyleneether) copolymer of claim 1 comprising a polysiloxane block comprisingthe structure

wherein n has an average value of 5-100, or 10-80 or 10-60.
 7. Thepoly(phenylene ether) copolymer of claim 1, wherein theC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group of the first repeating unitis a —C₁-C₃alkyl(bicyclo[2.2.1]heptene) group, a—C₁-C₃alkyl(bicyclo[2.2.1]heptadiene) group, a —C₁-C₃alkyl(cyclohexene)group, a —C₁-C₃alkyl(cyclohexadiene) group, or a —C₁-C₃alkyl(C₆₋₃₀cycloalkenyl) group, wherein the C₆₋₃₀ cycloalkenyl group is derivedfrom a terpene, each optionally substituted with a C₁₋₁₂ primary orsecondary hydrocarbyl, C₁₋₁₂ hydrocarbylthio, C₁₋₁₂ hydrocarbyloxy, or acombination thereof.
 8. The poly(phenylene ether) copolymer of claim 1,wherein the first repeating units are derived from2-CH₂(C₆₋₃₀cycloalkenyl)-6-methyl phenol,2-CH₂(C₆₋₃₀cycloalkenyl)-3,6-dimethyl phenol,3-CH₂(C₆₋₃₀cycloalkenyl)-2,6-dimethyl phenol,2-phenyl-6-CH₂(C₆₋₃₀cycloalkenyl) phenol, or a combination thereof.
 9. Amethod of preparing the poly(phenylene ether) copolymer of claim 1,comprising: reacting a cycloaddition monomer precursor comprising analkene or an alkyne with a conjugated diene via a cycloaddition reactionto provide a cycloaddition monomer product, wherein the cycloadditionmonomer precursor comprises a monohydric phenol, a dihydric phenol, abisphenol, or a combination thereof; oxidatively polymerizing thecycloaddition monomer product with an unsubstituted or substitutedmonohydric phenol, a dihydric phenol, a bisphenol, or a combinationthereof to provide a hydroxyl-terminated poly(phenylene ether) copolymerhaving an unsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl)pendant group; and optionally, reacting at least one hydroxyl terminalgroup of the hydroxyl-terminated poly(phenylene ether) copolymer havingan unsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀ cycloalkenyl) pendantgroup with a compound to provide poly(phenylene ether) copolymer havingan unsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendantgroup and at least one terminal functional group.
 10. A method ofpreparing the poly(phenylene ether) copolymer of any one of claim 1,comprising oxidatively polymerizing a polymerization precursorcomprising an alkene or alkyne with a monohydric phenol, a dihydricphenol, a bisphenol, or a combination thereof, to provide ahydroxyl-terminated polymerized intermediate, wherein the polymerizationprecursor comprises a monohydric phenol, a dihydric phenol, a bisphenol,or a combination thereof; reacting the hydroxyl-terminated polymerizedintermediate with a conjugated diene via a cycloaddition reaction toprovide a hydroxyl-terminated poly(phenylene ether) copolymer having anunsubstituted or substituted C₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group;and optionally, reacting at least one hydroxyl terminal group of thehydroxyl-terminated polymerized intermediate with a compound to providea poly(phenylene ether) copolymer having an unsubstituted or substitutedC₁₋₆alkyl(C₆₋₃₀cycloalkenyl) pendant group and at least one terminalfunctional group.
 11. A curable composition comprising thepoly(phenylene ether) copolymer of claim 1; and a curing promotercomprising an amine, a dicyandiamide, a polyamide, an amidoamine, aMannich base, an anhydride, a phenol-formaldehyde resin, a carboxylicacid functional polyester, a polysulfide, a polymercaptan, anisocyanate, a cyanate ester, or a combination thereof.
 12. The curablecomposition of claim 11, further comprising an auxiliary curable resincomprising an epoxy resin, a cyanate ester resin, a maleimide resin, abenzoxazine resin, a vinylbenzyl ether resin, an arylcyclobutene resin,a perfluorovinyl ether resin, oligomers or polymers with curable vinylfunctionality, or a combination thereof; a curable unsaturated monomercomprising a monofunctional styrenic compound, a monofunctional(meth)acrylic compound, a polyfunctional allylic compound, apolyfunctional (meth)acrylate, a polyfunctional (meth)acrylamide, apolyfunctional styrenic compound, or a combination thereof; or acombination thereof.
 13. A thermoset composition comprising the curablecomposition of claim 11, wherein the thermoset composition has a glasstransition temperature of greater than or equal to 180° C., asdetermined according to differential scanning calorimetry as per ASTMD3418 with a 20° C./min heating rate.
 14. An article comprising thethermoset composition of claim 13, wherein the article is a composite, afoam, a fiber, a layer, a coating, an encapsulant, an adhesive, asealant, a molded component, a prepreg, a casing, a laminate, a metalclad laminate, an electronic composite, or a structural composite.
 15. Amethod for the manufacture of a thermoset composition, the methodcomprising curing the curable composition of claim 11.